US4477424A - Continuous preparation of hydroxylammonium salts - Google Patents
Continuous preparation of hydroxylammonium salts Download PDFInfo
- Publication number
- US4477424A US4477424A US06/344,614 US34461482A US4477424A US 4477424 A US4477424 A US 4477424A US 34461482 A US34461482 A US 34461482A US 4477424 A US4477424 A US 4477424A
- Authority
- US
- United States
- Prior art keywords
- reaction zone
- nitric oxide
- acid
- last
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001272 nitrous oxide Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1418—Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen
Definitions
- the present invention relates to a process for the continuous preparation of hydroxylammonium salts by catalytic reduction of nitric oxide with hydrogen in a dilute aqueous solution of a mineral acid in the presence of a suspended noble metal catalyst at an elevated temperature in several reaction zones connected in series.
- this object is achieved by a process for the continuous preparation of hydroxylammonium salts by catalytic reduction of nitric oxide with hydrogen in a dilute aqueous solution of a mineral acid in the presence of a suspended noble metal catalyst at an elevated temperature in several reaction zones connected in series, wherein a pH of ⁇ 2.0 is maintained in the last reaction zone.
- the novel process has the advantages that increased formation of by-products is avoided in the last reaction zone, that no explosive off-gas mixtures are formed when it is carried out under superatmospheric pressure and, finally, that a sudden rise in pressure, which would adversely effect the preceding reaction zones also, is excluded.
- hydrogen and nitric oxide are used in a molar ratio of from 1.5 : 1 to 6 : 1. Particularly good results are obtained if a molar ratio of hydrogen to nitric oxide of from 3.5 : 1 to 5 : 1 is maintained in the individual reaction zones.
- the mineral acids used are non-reducing strong mineral acids, such as perchloric acid, nitric acid; sulfuric acid and phosphoric acid.
- Their acid salts for example ammonium bisulfate, can also be used. Sulfuric acid and/or ammonium bisulfate are particularly preferred.
- from 4 to 6 N aqueous solutions of the acids are used, and the acid concentration is allowed to decrease in the course of the reaction.
- the reaction is advantageously carried out at from 30° to 80° C., in particular from 40° to 60° C., and as a rule under atmospheric pressure or superatmospheric pressure, for example under a pressure of not more than 300 bar.
- Platinum catalysts are advantageously used as the noble metal catalysts, and are generally applied to carriers. Platinum on a carbon carrier, in particular on graphite, has proved especially suitable.
- the catalysts are used in finely divided form as a suspension, and preferably contain from 0.2 to 5 percent by weight of platinum.
- the catalysts advantageously also contain one or more elements of the 5th and/or 6th groups of the periodic table with an atomic weight of >31. Only phosphorus has an atomic weight of 31), as well as lead and/or mercury as poisons. Suitable catalysts and their preparation has been disclosed, for example, in German Pat. Nos. 1,088,037, 920,963, 956,038 and 945,752.
- reaction zone is carried out in several reaction zones connected in series. From 2 to 10, in particular from 4 to 8, reaction zones are as a rule used, and these advantageously communicate with one another.
- fresh dilute aqueous solution of mineral acid containing the suspended catalyst is fed to the first reaction zone, and then flows through the individual reaction zones in succession, the content of hydroxylammonium salt progressively increasing as the acid is consumed.
- the reaction mixture is removed from the last reaction zone at a rate corresponding to that at which fresh aqueous acid is fed into the first reaction zone.
- the reaction zones are each separately charged with a mixture of nitric oxide and hydrogen, with the exception of the first zone, and the off-gases formed are collected and introduced into the first reaction zone, advantageously after replenishing with nitric oxide.
- a pH of ⁇ 2.0 advantageously of from 0.9 to 1.8
- the last reaction zone i.e. in the reaction mixture substantially consisting of an aqueous solution of hydroxylammonium salts, ammonium salts, acid, supported catalyst and dissolved nitric oxide.
- the pH in the last reaction zone is brought to this level, for example, by increased or reduced addition of nitric oxide and hydrogen, or by the batchwise or continuous addition of further acid, which is advantageously controlled via the pH in the last reaction zone. It has proved particularly advantageous to control the flow of fresh aqueous mineral acid into the first reaction zone via the pH in the last reaction zone. If sulfuric acid is used, this pH is advantageously kept at from 1.0 to 1.5.
- Control of the flow of fresh mineral acid via the pH in the last reaction zone is noteworthy in that, as a result of the long residence time, no rapid effect on the pH of the last reaction zone was to be expected. Rather, it was to be assumed that wide variations in the pH would occur in the last reaction zone.
- the last-mentioned procedure also has the particular advantage that on the one hand the disadvantages mentioned initially are avoided, and on the other hand an excessive residual content of mineral acid, which is undesirable for the further processing of the hydroxylammonium salt solution, is also avoided.
- Hydroxylammonium salts which are obtained by the process of the invention can be used for the preparation of cyclohexanone oxime, a starting compound for the preparation of caprolactam.
- Nitric oxide and hydrogen are added separately to each of reactors 2 to 8, and the off-gasses are collected and, after being replenished with nitric oxide, are recycled to reactor 1.
- the reaction is carried out at 40° C. and under 1 bar.
- Reaction mixture is continuously removed from reactor 8, via an external loop, and its pH is measured.
- the pH reaches 1.3
- the amount of sulfuric acid flowing into reactor 1 is increased by means of a regulator connected to the pH meter.
- the pH of the reaction mixture in reactor 8 reaches 1.1
- the amount of sulfuric acid flowing into reactor 1 is reduced via the regulator.
- the off-gas formed in reactor 8 contains 10% by volume of nitrous oxide, and the reaction mixture flowing out contains 0.1 percent by weight of ammonium sulfate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An improved process for the continuous preparation of hydroxylammonium salts by catalytic reduction of nitric oxide with hydrogen in a dilute aqueous solution of a mineral acid in the presence of a suspended noble metal catalyst at an elevated temperature in several reaction zones connected in series, wherein the improvement comprises maintaining a pH of <2.0 in the last reaction zone.
Description
The present invention relates to a process for the continuous preparation of hydroxylammonium salts by catalytic reduction of nitric oxide with hydrogen in a dilute aqueous solution of a mineral acid in the presence of a suspended noble metal catalyst at an elevated temperature in several reaction zones connected in series.
The preparation of hydroxylammonium salts by catalytic reduction of nitric oxide with hydrogen in dilute aqueous solutions of mineral acids in the presence of a suspended noble metal catalyst is a conventional process and is carried out industrially. A continuous procedure is described, for example, in German Pat. No. 1,177,118. In this procedure, an aqueous solution of mineral acid containing the suspended catalyst is passed through several stirred kettles connected in series, a mixture of nitric oxide and hydrogen is passed into each stirred kettle and a hydroxylammonium salt solution which contains catalyst is removed from the last stirred kettle. It has been found that a rise in pressure, with increased formation of nitrous oxide and nitrogen, and increased formation of ammonium salts frequently occur in the last stirred kettle. Apart from the fact that increased formation of gaseous by-products is undesirable, there is the danger of an explosive mixture being formed on increased formation of nitrous oxide, especially if the process is being carried out under superatmospheric pressure. Increased formation of ammonium salts is also undesirable, since the yield of hydroxylammonium salts falls and moreover unwanted quantities of ammonium salts must be separated off during further processing.
It is an object of the present invention to carry out continuous preparation of hydroxylammonium salts in several reaction zones, connected in series, in such a way that increased formation of by-products is avoided, even in the last reaction zone.
We have found that this object is achieved by a process for the continuous preparation of hydroxylammonium salts by catalytic reduction of nitric oxide with hydrogen in a dilute aqueous solution of a mineral acid in the presence of a suspended noble metal catalyst at an elevated temperature in several reaction zones connected in series, wherein a pH of <2.0 is maintained in the last reaction zone.
The novel process has the advantages that increased formation of by-products is avoided in the last reaction zone, that no explosive off-gas mixtures are formed when it is carried out under superatmospheric pressure and, finally, that a sudden rise in pressure, which would adversely effect the preceding reaction zones also, is excluded.
As a rule, hydrogen and nitric oxide are used in a molar ratio of from 1.5 : 1 to 6 : 1. Particularly good results are obtained if a molar ratio of hydrogen to nitric oxide of from 3.5 : 1 to 5 : 1 is maintained in the individual reaction zones.
In general, the mineral acids used are non-reducing strong mineral acids, such as perchloric acid, nitric acid; sulfuric acid and phosphoric acid. Their acid salts, for example ammonium bisulfate, can also be used. Sulfuric acid and/or ammonium bisulfate are particularly preferred. As a rule, from 4 to 6 N aqueous solutions of the acids are used, and the acid concentration is allowed to decrease in the course of the reaction.
The reaction is advantageously carried out at from 30° to 80° C., in particular from 40° to 60° C., and as a rule under atmospheric pressure or superatmospheric pressure, for example under a pressure of not more than 300 bar.
Platinum catalysts are advantageously used as the noble metal catalysts, and are generally applied to carriers. Platinum on a carbon carrier, in particular on graphite, has proved especially suitable. The catalysts are used in finely divided form as a suspension, and preferably contain from 0.2 to 5 percent by weight of platinum. The catalysts advantageously also contain one or more elements of the 5th and/or 6th groups of the periodic table with an atomic weight of >31. Only phosphorus has an atomic weight of 31), as well as lead and/or mercury as poisons. Suitable catalysts and their preparation has been disclosed, for example, in German Pat. Nos. 1,088,037, 920,963, 956,038 and 945,752.
The reaction is carried out in several reaction zones connected in series. From 2 to 10, in particular from 4 to 8, reaction zones are as a rule used, and these advantageously communicate with one another. Advantageously, fresh dilute aqueous solution of mineral acid containing the suspended catalyst is fed to the first reaction zone, and then flows through the individual reaction zones in succession, the content of hydroxylammonium salt progressively increasing as the acid is consumed. The reaction mixture is removed from the last reaction zone at a rate corresponding to that at which fresh aqueous acid is fed into the first reaction zone. Advantageously, the reaction zones are each separately charged with a mixture of nitric oxide and hydrogen, with the exception of the first zone, and the off-gases formed are collected and introduced into the first reaction zone, advantageously after replenishing with nitric oxide.
It is an essential characteristic of the invention that a pH of <2.0, advantageously of from 0.9 to 1.8, is maintained in the last reaction zone, i.e. in the reaction mixture substantially consisting of an aqueous solution of hydroxylammonium salts, ammonium salts, acid, supported catalyst and dissolved nitric oxide. The pH in the last reaction zone is brought to this level, for example, by increased or reduced addition of nitric oxide and hydrogen, or by the batchwise or continuous addition of further acid, which is advantageously controlled via the pH in the last reaction zone. It has proved particularly advantageous to control the flow of fresh aqueous mineral acid into the first reaction zone via the pH in the last reaction zone. If sulfuric acid is used, this pH is advantageously kept at from 1.0 to 1.5. Control of the flow of fresh mineral acid via the pH in the last reaction zone is noteworthy in that, as a result of the long residence time, no rapid effect on the pH of the last reaction zone was to be expected. Rather, it was to be assumed that wide variations in the pH would occur in the last reaction zone. The last-mentioned procedure also has the particular advantage that on the one hand the disadvantages mentioned initially are avoided, and on the other hand an excessive residual content of mineral acid, which is undesirable for the further processing of the hydroxylammonium salt solution, is also avoided.
Hydroxylammonium salts which are obtained by the process of the invention can be used for the preparation of cyclohexanone oxime, a starting compound for the preparation of caprolactam.
The Example which follows illustrates the process of the invention.
Eight reaction vessels connected in series are each charged with 6,000 l of 4.5 N sulfuric acid and 150 kg of a platinum-on-graphite catalyst containing 1 percent by weight of platinum. With the connecting lines closed, the reaction vessels are charged with a mixture of hydrogen and nitric oxide in a molar ratio of 1.7 : 1, so that the concentration of free sulfuric acid decreases from vessel to vessel. The connecting lines between the individual reaction vessels are then opened, and 4.5 N sulfuric acid and platinum catalyst are introduced into the first reactor, whilst the corresponding amount of hydroxylammonium sulfate solution and catalyst is removed from the eighth reactor. The catalyst is filtered off and added to the fresh sulfuric acid. Nitric oxide and hydrogen are added separately to each of reactors 2 to 8, and the off-gasses are collected and, after being replenished with nitric oxide, are recycled to reactor 1. The reaction is carried out at 40° C. and under 1 bar. Reaction mixture is continuously removed from reactor 8, via an external loop, and its pH is measured. As soon as the pH reaches 1.3, the amount of sulfuric acid flowing into reactor 1 is increased by means of a regulator connected to the pH meter. When the pH of the reaction mixture in reactor 8 reaches 1.1, the amount of sulfuric acid flowing into reactor 1 is reduced via the regulator. The off-gas formed in reactor 8 contains 10% by volume of nitrous oxide, and the reaction mixture flowing out contains 0.1 percent by weight of ammonium sulfate.
If the pH in reactor 8 rises to 2.0, the content of nitrous oxide in the off-gas is increased to 15% by volume and the content of ammonium sulfate in the reaction solution discharged is increased to 0.2 percent by weight.
Claims (1)
1. In a process for the continuous preparation of hydroxylammonium salts by the catalytic reduction of nitric oxide with hydrogen in a dilute aqueous solution of a mineral acid in the presence of a suspended noble metal catalyst at an elevated temperature in from 4 to 8 reaction zones connected in series, the improvement comprising: continuously monitoring the pH in the last reaction zone and, in response thereto, adding sufficient fresh aqueous acid to the first reaction zone to maintain the pH in the last reaction zone between 0.9 and 1.8, whereby the increased formation of by-products and an excessive content of mineral acid is avoided in the last reaction zone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813107702 DE3107702A1 (en) | 1981-02-28 | 1981-02-28 | METHOD FOR THE CONTINUOUS PRODUCTION OF HYDROXYLAMMONIUM SALTS |
| DE3107702 | 1981-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4477424A true US4477424A (en) | 1984-10-16 |
Family
ID=6126047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/344,614 Expired - Lifetime US4477424A (en) | 1981-02-28 | 1982-02-01 | Continuous preparation of hydroxylammonium salts |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4477424A (en) |
| EP (1) | EP0059366B1 (en) |
| JP (1) | JPS57156312A (en) |
| DE (2) | DE3107702A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554353A (en) * | 1994-02-04 | 1996-09-10 | Basf Aktiengesellschaft | Preparation of hydroxylammonium salts |
| US20040018136A1 (en) * | 2000-12-14 | 2004-01-29 | Michael Bender | Method for continuous producing hydroxylammonium salts |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0613171A2 (en) * | 2005-07-08 | 2010-12-21 | Dsm Ip Assets Bv | process and equipment for the continuous production of hydroxylammonium |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE920963C (en) * | 1953-02-25 | 1954-12-06 | Basf Ag | Process for the preparation of hydroxylammonium salts |
| DE945752C (en) * | 1954-05-14 | 1956-07-19 | Basf Ag | Process for the preparation of hydroxylammonium salts |
| DE956038C (en) * | 1954-04-01 | 1957-01-10 | Basf Ag | Process for the preparation of hydroxylammonium salts |
| DE968363C (en) * | 1949-08-27 | 1958-02-06 | Du Pont | Process for the preparation of salts of hydroxylamine |
| DE1088037B (en) * | 1957-10-23 | 1960-09-01 | Basf Ag | Process for the production and regeneration of a special catalyst for the production of hydroxylamine |
| DE1177118B (en) * | 1963-03-08 | 1964-09-03 | Basf Ag | Process for the continuous production of hydroxylammonium salts |
| DE1193923B (en) * | 1962-07-13 | 1965-06-03 | Inventa A G Fuer Forschung | Process for the production of hydroxylamine |
| DE1567832A1 (en) * | 1965-05-03 | 1970-08-20 | Stamicarbon | Process for the preparation of a solution containing hydroxylammonium salt |
| DE2046197A1 (en) * | 1969-09-20 | 1971-04-01 | Stamicarbon N V , Heerlen (Nieder lande) | Process for the continuous production of a hydroxylammonium salt-containing solution in water |
| US4048291A (en) * | 1974-05-10 | 1977-09-13 | Inventa Ag Fur Forschung Und Patentverwertung | Process for preparing hydroxylammonium salts |
| US4192856A (en) * | 1977-08-16 | 1980-03-11 | Basf Aktiengesellschaft | Manufacture of hydroxylammonium salts |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5521775B2 (en) * | 1972-10-18 | 1980-06-12 | ||
| DE2743297C2 (en) * | 1977-09-27 | 1979-11-22 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of hydroxyl anunonium salts |
-
1981
- 1981-02-28 DE DE19813107702 patent/DE3107702A1/en not_active Withdrawn
-
1982
- 1982-02-01 US US06/344,614 patent/US4477424A/en not_active Expired - Lifetime
- 1982-02-17 EP EP82101158A patent/EP0059366B1/en not_active Expired
- 1982-02-17 DE DE8282101158T patent/DE3264817D1/en not_active Expired
- 1982-02-22 JP JP57026166A patent/JPS57156312A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE968363C (en) * | 1949-08-27 | 1958-02-06 | Du Pont | Process for the preparation of salts of hydroxylamine |
| DE920963C (en) * | 1953-02-25 | 1954-12-06 | Basf Ag | Process for the preparation of hydroxylammonium salts |
| DE956038C (en) * | 1954-04-01 | 1957-01-10 | Basf Ag | Process for the preparation of hydroxylammonium salts |
| DE945752C (en) * | 1954-05-14 | 1956-07-19 | Basf Ag | Process for the preparation of hydroxylammonium salts |
| DE1088037B (en) * | 1957-10-23 | 1960-09-01 | Basf Ag | Process for the production and regeneration of a special catalyst for the production of hydroxylamine |
| DE1193923B (en) * | 1962-07-13 | 1965-06-03 | Inventa A G Fuer Forschung | Process for the production of hydroxylamine |
| DE1177118B (en) * | 1963-03-08 | 1964-09-03 | Basf Ag | Process for the continuous production of hydroxylammonium salts |
| DE1567832A1 (en) * | 1965-05-03 | 1970-08-20 | Stamicarbon | Process for the preparation of a solution containing hydroxylammonium salt |
| DE2046197A1 (en) * | 1969-09-20 | 1971-04-01 | Stamicarbon N V , Heerlen (Nieder lande) | Process for the continuous production of a hydroxylammonium salt-containing solution in water |
| US4048291A (en) * | 1974-05-10 | 1977-09-13 | Inventa Ag Fur Forschung Und Patentverwertung | Process for preparing hydroxylammonium salts |
| US4192856A (en) * | 1977-08-16 | 1980-03-11 | Basf Aktiengesellschaft | Manufacture of hydroxylammonium salts |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554353A (en) * | 1994-02-04 | 1996-09-10 | Basf Aktiengesellschaft | Preparation of hydroxylammonium salts |
| US20040018136A1 (en) * | 2000-12-14 | 2004-01-29 | Michael Bender | Method for continuous producing hydroxylammonium salts |
| US7037478B2 (en) | 2000-12-14 | 2006-05-02 | Basf Aktiengesellschaft | Method for continuous producing hydroxylammonium salts |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0059366A1 (en) | 1982-09-08 |
| JPS57156312A (en) | 1982-09-27 |
| DE3264817D1 (en) | 1985-08-29 |
| DE3107702A1 (en) | 1982-09-16 |
| EP0059366B1 (en) | 1985-07-24 |
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